Catalytic dehalogenation of alpha-halogenated carboxylic acids/esters

ABSTRACT

The alpha-halogenated carboxylic acids/esters are dehalogenated by reaction with hydrogen in the presence of a catalytically effective amount of (i) a Group VIII precious metal catalyst and (ii) either sulfur or a sulfur compound, or (iii) a novel precious metal/sulfur solid phase catalyst; the subject dehalogenation is especially adapted for enriching the monochloroacetic acid content of MCAA/DCAA mixtures.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to the catalytic dehalogenation of alpha-halogenated carboxylic acids, and, more especially, to the selective catalytic dehalogenation of the dichloroacetic acid (DCAA) fraction present in monochloroacetic acid (MCAA).

2. Description of the Prior Art

The synthesis of monochloroacetic acid is carried out on an industrial scale by the chlorination of acetic acid, but dichloroacetic acid and sometimes a minor amount of trichloroacetic acid are also unavoidably formed. Therefore, upon completion of the chlorination reaction, a mixture of monochloroacetic acid, dichloroacetic acid, trichloroacetic acid and unreacted acetic acid is characteristically produced.

Because of the proximity of the boiling points of MCAA (189° C.) and of DCAA (194° C.), it is practically impossible to separate these species by distillation. On the other hand, it is quite simple to hydrogenate such a mixture to convert the DCAA into MCAA according to the reaction:

    CHCl.sub.2 COOH+H.sub.2 →CH.sub.2 ClCOOH+HCl

But this hydrogenation is not completely selective and a reversion of MCAA to acetic acid is also observed, as follows:

    CH.sub.2 ClCOOH+H.sub.2 →CH.sub.3 COOH+HCl

This reaction is carried out in the presence of a catalyst and also produces acetaldehyde, which has the disadvantage of giving rise to objectionable condensation products.

FR 1,581,391 describes such a process based on a catalyst of silica in the form of cylinders 8 mm in length and 3.5 mm in diameter, which has a palladium content of 0.5% by weight.

FR 2,039,987 describes a process of the same type as the above, but entailing introduction of either salts or oxides of the alkali or alkaline earth metals or of rare earths, or an organic compound designated a proton-acceptor, which may be, for example, triethylamine, pyridine, piperidine, glycine, urea, triphenylphosphine, butyraldehyde, diisobutyl ketone, butyl acetate or hydrocyanic acid. This catalyst activator is introduced into the mixture to be hydrogenated and can be recovered by distillation of the hydrogenated mixture. It can be recycled into the mixture to be hydrogenated.

SUMMARY OF THE INVENTION

Accordingly, a major object of the present invention is the provision of an improved process for the catalytic dehalogenation of alpha-halogenated carboxylic acids in the presence of an activator, such catalyst activation being long-lived and even continuing, in modified state, after introduction of the activator into the mixture to be hydrogenated has been terminated.

Another object of the present invention is the provision of an improved process for the selective catalytic hydrogenation of the di- and tri-alpha-halogenated carboxylic acids.

Yet another object of this invention is the provision of an improved process for the catalytic dehalogenation of alpha-halogenated carboxylic acids while minimizing by-production of the corresponding aldehydes.

Another object of this invention is the provision of an improved hydrogenation/dehalogenation catalyst, per se.

Briefly, the present invention features a process for the dehalogenation of alpha-halogenated carboxylic acids, or esters thereof, comprising reacting such acids/esters with hydrogen in the presence of a catalyst based on a precious metal of Group VIII of the Periodic Table, and wherein such catalytic dehalogenation is carried out in the presence of sulfur or a sulfur compound.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS OF THE INVENTION

More particularly according to the present invention, and while it is applicable to any alpha-halogenated carboxylic acids, the preferred acids have the formula: ##STR1## in which X is chlorine or bromine, and R₁ and R₂, which may be identical or different, are each X, H, a linear or branched chain alkyl radical having from 1 to 12 carbon atoms, or a cycloalkyl radical having from 3 to 12 carbon atoms. The invention is also applicable to the esters of the acids of formula (I); these are preferably aliphatic esters having from 1 to 10 carbon atoms and preferably from 1 to 5 carbon atoms.

According to this invention, the dehalogenation of a single acid or of a mixture of acids may be carried out. These acids may also be in admixture with a solvent.

The precious metals of Group VIII of the Periodic Table include ruthenium, rhodium, palladium, osmium, iridium and platinum. The first three are advantageously employed, and preferably palladium. These metals may be employed by themselves, as alloys, or mixed with each other. They may be employed as such, or deposited onto a support, for example charcoal, silica, silicon carbide or boron carbide.

The catalyst may be employed in the form of fine particles, namely, the acids and the catalyst are mixed, sulfur is added and hydrogen is introduced.

Depending on the end applications for the dehalogenated acids, it is sometimes necessary to separate the catalyst from the acids upon completion of dehalogenation. In a preferred embodiment of the invention, the catalyst is arranged as a stationary bed or as a fluid bed, in a vessel, and the acids to be dehalogenated, the hydrogen and the sulfur are introduced into this vessel. It is therefore not necessary to separate the catalyst upon completion of dehalogenation. A catalyst is preferably employed as a stationary bed and the operation is continuous.

The precious metal is advantageously deposited onto a charcoal having a large surface area, in a proportion of 0.3 to 1% by weight of the catalyst, namely, of the charcoal plus the metal, and it is distributed over the surface of the charcoal. A charcoal having a large surface area is one having a surface area of approximately 600 m² /g and even up to 1,300 m² /g. This charcoal is advantageously in the form of small extruded cylinders or of a powder of approximately 50μ. The amount of catalyst is easily determined by one skilled in this art.

Sulfur or sulfur compounds are advantageously added into the acids to be dehalogenated. Exemplary sulfur compounds are SCl₂, S₂ Cl₂, CS₂, thiophene, or sulfur/oxygen compounds. The sulfur or the sulfur compounds are added in the form of minor amounts of up to 1 g per kg of acid or of the mixture containing the acids to be hydrogenated, and preferably from 0.1 to 200 mg/kg, expressed as sulfur.

It is advantageous to carry out the process of the invention with the acids in liquid phase. Although it is possible to operate at any temperature, it is advantageous to utilize a temperature ranging from that at which the acids are liquid to 200° C., and preferably from 100° to 180° C. If necessary, the acid(s) may be dissolved in a solvent to permit operation within this preferred temperature range.

The process may be carried out at atmospheric pressure or at a pressure of up to 5 bars. The effect of pressure is to increase the reaction kinetics; since the acids are corrosive and also the reaction medium of the invention, it is not judicious to exceed a pressure on the order of 5 bars.

The invention is particularly useful for purifying impure mono-alpha-halogenated carboxylic acids R₁ CHXCOOH, wherein R₁ is as defined above. These acids are prepared by halogenation of the corresponding acid R₁ CH₂ COOH; a mixture of R₁ CHXCOOH, of R₁ CX₂ COOH, of unconverted acid R₁ CH₂ COOH is obtained, sometimes including trace amounts of CX₃ COOH in the particular case of acetic acid, CH₃ COOH.

R₁ CH₂ COOH could first be separated from this mixture, but it is simpler to conduct the hydrogenation:

    R.sub.1 CX.sub.2 COOH+H.sub.2 →R.sub.1 CHXCOOH+HX

and then to separate the nonhalogenated acid, since unavoidably a fraction of the R₁ CHXCOOH is converted back into such acid according to the reaction scheme:

    R.sub.1 CHXCOOH+H.sub.2 →R.sub.1 CH.sub.2 COOH+HX

It then suffices to distill the mixture of R₁ CHXCOOH, of R₁ CH₂ COOH and of HX, to obtain relatively pure R₁ CHXCOOH.

The invention is particularly applicable to the purification of monochloroacetic acid.

The dehalogenation is characteristically commenced with the catalyst alone, without the sulfur values. The sulfur is then introduced and a few hours later, while the sulfur is still being introduced, a slightly lower conversion of R₁ CX₂ COOH is observed at the same temperature, a much lower reversion and a large decrease in the byproduct aldehyde R₁ CH₂ CHO.

The reversion is the ratio between the number of X⁻ ions in the purified acid, i.e., those originating from HX to the theoretical number of X to be removed from R₁ CX₂ COOH (and possibly CX₃ COOH) to convert it into R₁ CHXCOOH. With the exception of CX₃ COOH, the minimum reversion is 1. This reversion in most cases ranges from 1.4 to 3.4.

Unexpectedly, it has now surprisingly been found that when the introduction of sulfur is terminated, its effects continued in a relatively unmodified form, namely, the conversion of R₁ CX₂ COOH increases again and exceeds that of the prior art, the reversion increases again and ranges from the above value to that of the prior art, the aldehyde level increases again and is also situated between the above value and that of the prior art.

The process can be continued while resuming the introduction of the sulfur (which had been terminated); a return to the values observed during the initial introduction of the sulfur is determined.

It has also been determined that the catalyst based on a precious metal was converted into a catalyst based on a solid phase of sulfur and of the precious metal. Thus, the present invention also features such novel catalyst, per se. This catalyst is advantageously a solid phase of sulfur and of palladium deposited onto a support which may be charcoal, silica, silicon carbide or boron carbide.

This catalyst is preferably Pd₄ S deposited onto charcoal.

The present invention also features a process for the dehalogenation of alpha-halogenated carboxylic acids, or esters thereof, by reacting such acids/esters with hydrogen in the presence of a catalyst comprising a solid phase of sulfur and of a precious metal of Group VIII.

In this process employing such solid phase, it is also possible to continue to add the sulfur, advantageously in the feedstream of the acids to be dehalogenated. At the outlet of the reactor, the sulfur is recovered in the dehalogenated acids in the form of compounds which can be removed by distillation. The operating conditions are the same as those described above. This process employing the catalyst which is a sulfur/precious metal solid phase, in combination with an addition of sulfur or otherwise, can also be used for purifying the acids R₁ CHXCOOH, and in particular monochloroacetic acid.

In order to further illustrate the present invention and the advantages thereof, the following specific examples are given, it being understood that same are intended only as illustrative and in nowise limitative.

EXAMPLE 1

A jacketed glass column A, 26 mm in internal diameter, was charged with 300 cm³ of an extruded charcoal 2 mm in diameter and 4 mm in length, having a specific surface area>700 m² /g and containing 0.8% of palladium deposited at the surface (>100 m² /g of palladium).

This column was then concurrently charged with an acid solution (in % by weight): approximately 80% monochloroacetic acid, approximately 4% dichloroacetic acid, approximately 16% acetic acid, and with a hydrogen stream of 4 normal liters per hour.

The temperature of the column was increased, to 125° C., and after a period of time to equilibrate the reaction conditions, feed changes were carried out and the results reported in Table I were observed.

The column was charged with a liquid containing 30 ppm of sulfur from the 187th hour to the 355th hour.

The results are reported in Table I:

The "hours of operation" denote the cumulative hours from time 0;

LSV denotes the liquid space velocity.

A determination of sulfur int he MCAA at the outlet of the column was made at the 350th hour; 29 ppm were found.

X-ray diffraction analysis of catalyst granules removed after the 350th hour evidenced the presence of Pd₄ S and the absence of Pd.

                  TABLE I                                                          ______________________________________                                         Hours of                                                                              L.S.V.    Outlet    CH.sub.3 CHO                                        operation                                                                             kg/h m.sup.3                                                                             DCAA %    formed mg/kg                                                                             Reversion                                 ______________________________________                                         165    245       0.12      1185      3                                         187    235       0.13      307       1.77                                      211    234       0.22      238       1.73                                      284    244       0.3       242       1.87                                      355    244       0.33      232       1.84                                      379    243       0.25      416       1.90                                      413    251       0.08      656       2.30                                      442    244       0.06      776       2.42                                      468    244       0.08      786       2.30                                      540    249       <0.03     982       2.14                                      COLUMN STOPPED                                                                 ______________________________________                                    

EXAMPLE 2

The procedure of Example 1 was repeated with a column B identical with A, but using S₂ Cl₂ (30 ppm as S) between the 353rd hour and the 616th hour. The results are reported in Table II:

                  TABLE II                                                         ______________________________________                                         Hours of                                                                              L.S.V.    Outlet    CH.sub.3 CHO                                        operation                                                                             kg/h m.sup.3                                                                             DCAA %    formed mg/kg                                                                             Reversion                                 ______________________________________                                         165    247       0.21      1513      3.05                                      189    241       0.16      1371      3.09                                      252    243       0.12      1366      3.37                                                       0.16      1243      3.28                                      350    249       0.07      1321      2.61                                      353                                                                            374    242       0.15      323       1.5                                       422    234       0.20      274       1.48                                      518    233       0.20      295       1.40                                      568    210       0.13      287       1.44                                      616    215       0.17      256       1.40                                      663    246       0.14      690       1.91                                      758    237       0.11      938       2.28                                      ______________________________________                                    

Catalyst granules were removed after the 400th hour and, as in Example 1, only Pd₄ S was found therein.

EXAMPLE 3

Column A was used as in Example 1 with the catalyst that had been used in Example 1, but between the 685th and 827th hour 36 ppm of carbon sulfide were added to the impure MCAA. The results are reported in Table III:

                  TABLE III                                                        ______________________________________                                         Hours of                                                                              L.S.V.    Outlet    CH.sub.3 CHO                                        operation                                                                             kg/h m.sup.3                                                                             DCAA %    formed mg/kg                                                                             Reversion                                 ______________________________________                                         590    247       <0.03     951       2.25                                      685    234       <0.03     1174      2.47                                      709    250       0.05      307       1.56                                      755    253       0.08      276       1.55                                      803    236       0.06      289       1.63                                      827    245       0.08      247       1.63                                      ______________________________________                                    

The sulfur determined at the column outlet during the injection of CS₂ was approximately 27 mg/kg.

While the invention has been described in terms of various preferred embodiments, the skilled artisan will appreciate that various modifications, substitutions, omissions, and changes may be made without departing from the spirit thereof. Accordingly, it is intended that the scope of the present invention be limited solely by the scope of the following claims, including equivalents thereof. 

What is claimed is;
 1. A process for the dehalogenation of an alpha-halogenated carboxylic acid, or ester thereof, comprising reacting such acid or ester with hydrogen int he presence of a catalytically effective amount of (i) a Group VIII precious metal catalyst, and (ii) either sulfur or a sulfur compound.
 2. A process for the dehalogenation of an alpha-halogenated carboxylic acid as defined by claim 1, said carboxylic acid having the formula (I): ##STR2## wherein X is chlorine or bromine, and R₁ and R₂, which may be identical or different, are each X, H, a linear or branched chain alkyl radical having from 1 to 12 carbon atoms, or a cycloalkyl radical having from 3 to 12 carbon atoms.
 3. The dehalogenation process as defined by claim 1, said precious metal catalyst comprising palladium deposited onto a charcoal support.
 4. The dehalogenation process as defined by claim 3, said precious metal catalyst comprising from 0.3 to 1% by weight of palladium.
 5. The dehalogenation process as defined by claim 1, carried out int he presence of (ii) a sulfur compound.
 6. The dehalogenation process as defined by claim 5, said sulfur compound comprising S₂ Cl₂ or CS₂.
 7. The dehalogenation process as defined by claim 1, wherein the amount of sulfur or a sulfur compound, expressed as elemental sulfur ranges from 0.1 to 200 mg/kg of the acid or ester to be hydrogenated.
 8. A process for enriching the monochloroacetic acid content of a mixture thereof with dichloroacetic acid and, optionally, acetic acid, comprising selectively hydrogenating such mixture in the presence of a catalytically effective amount of (i) a Group VIII precious metal catalyst, and (ii) either sulfur or a sulfur compound.
 9. A process for the dehalogenation of an alphahalogenated carboxylic acid, or ester thereof, comprising reacting such acid or ester with hydrogen in the presence of a catalytically effective amount of a catalyst comprising a solid palladium phase, Pd₄ S, deposited onto a charcoal support.
 10. The dehalogenation process as defined by claim 9, carried out in the further presence of sulfur or a sulfur compound.
 11. A process for enriching the monochloroacetic acid content of a mixture thereof with dichloroacetic acid and, optionally, acetic acid, comprising selectively hydrogenating such mixture in the presence of a catalystically effective amount of a catalyst comprising a solid palladium phase, Pd₄ S, deposited onto a charcoal support.
 12. The enrichment process as defined by claim 11, carried out in the further presence of sulfur or a sulfur compound.
 13. The dehalogenation process as defined by claim 1, said precious metal catalyst comprising ruthenium, rhodium or palladium.
 14. The dehalogenation process as defined by claim 3, said charcoal support having a surface area ranging from about 600 m² /g to 1,300 m² /g. 